Preparation of amino products from cyclododecatriene-1, 5, 9



United States Patent 3,118,938 PREPARATION OF AMINO PRODUCTS FROMCYCLODODECATRIENE-1,5,9 Archibald P. Stuart, Media, and Charles E.Scott, Drexel Hill, Pa., assignors to Sun Oil Company, Philadelphia,Pa., a corporation of New Jersey No Drawing. Filed Nov. 28, 1962, Ser.No. 240,708 7 Claims. (Cl. 260-563) This invention relates to thereaction of cyclododecatriene-1,5,9 to form novel amino compounds whichare reaction products between dicyclic conjugated diene prodnot formedas an intermediate in the reaction and N-lithio primary aliphaticrdia'mine used in the reaction.

It is known that cyclododecatriene-1,5,9 can be prepared by contactingbutadiene with a catalyst formed from titanium tetrachloride and diethylaluminum chloride in a hydrocarbon solvent. This catalyst systemproduccs the trans-trans-cis form of the triene. It is also known thatcyclododecatriene-1,5,9 can be prepared by contacting butadiene with acatalyst system which is aluminum triethyl together with either chromylchloride or chromic chloride in a hydrocarbon solvent. The latter typeof catalyst system produces mainly the trans-transtrans form of thetriene but also causes the formation of substantial amounts of thetrans-trans-cis isomer.

The present invention provides a method for converting either form ofcyclododecatriene-1,5,9 into novel amino compounds which are reactionproducts between bicycle-[ .5 .0]-dodecadiene, which is formed as anintermediate in the reaction, and =N-lithio primary aliphatic di aminewhich functions both as a catalyst and reactant during the reaction. Thebicyclodiene intermediate is a result of structural rearrangement of thecyclododecatriene- 1,5,9 and comprises two conjugated isomers asfollows:

A. Bicyclo- 5 .5 .O'] 1 ,7-'do deoadiene:

H 0 OIHZ o o H H; B. Bicycle-[5 .5.0]-A -dodecadiene:

In In During the reaction one or both of these conjugated isomers reactWith the N-lithio aliphatic diamine to form amino products. A lowerboiling amino product is formed which has one (w-aminoalkyl) amino groupattached to the bicyolo hydrocarbon nucleus. This mono-addition productappears to be at least mainly the reaction product of isomer B, ha vingthe (w-ami-noalkyl) amino group attached primarily at the 3-positionalthough some addition at the 2-position may also occur. There is alsoproduced higher boiling amino material which may be a bis-additionproduct formed by reaction at the two double bond positions of isomer Aand thus having (w-aminoalkyl) amino groups attached at both the2-position and 8-pos-ition. However it is not known with certaintywhether the higher boiling amino material is a result of this or someother reaction mechanism. in any event both relatively low androllaitiyely [high boiling amino products are obtained. These aminoproducts are good emulsifiers and can be used in preparing variousemulsified products and as ore flotation agents.

3,118,938 Patented Jan. 21, 1964 According to one embodiment of theinvention, cyclododecatriene-1,5,9 is converted to amino derivatives ofbicycle[5.5.01-dodecadiene by contacting the triene at an elevatedtemperature with a catalyst system comprising N-lithioethylene diamine(H NCH CH NHLi) dissolved in ethylene diarnine. This system can beprepared by reacting lithium metal with an excess of ethylene diamine atan elevated temperature, for example, 90110 C., until all of the lithiumhas gone into solution. Conversion of the cyclododeoatriene-1,5,9 iseffected by mixing it with the resulting catalyst system and maintainingthe mixture at a temperature in the range of 50-200 C., more preferablyl20 C. for a time sufilcient to ellect substantial conversion. Underthese conditions the cyolododecatniene- 1,5,9 rearranges to produce thediene isomers shown above and the hydrocarbon prod-uct further reacts inthe presence of the catalyst system to produce material having one ofthe nitrogen atoms from the diamin-e bonded to a ring carbon atom of thehydrocarbon intermediate. The exact mechanism of this reaction is notknown with certainty but is thought that the intermediate hydrocarbonproduct reacts with the N-lithioethylene diamine, following which aninterchange between lithium and hydrogen of the excess ethylene diamineoccurs to produce additional amounts of N-lithioethylene diamine. In anyevent, the overall effect is to combine ethylene diarnine with theconjugated diene intermediate material to produce the amino products.

The final reaction mixture generally contains, in addition to the aminoproducts, unreacted 'bicyclo hydro carbon isomers referred to above andit may also contain an amount of unconverted cyclododeoatriene. It alsogenerally contains a substantial amount of polymeric hydrocarbonproduct. The yield of amino product resulting from the reaction varieswith changes in reaction conditions. Formation of the amino product isfavored by increasing reaction time, increasing the amount of excessethylene diamine and increasing reaction temperature. In order toincrease the rate of reaction the lithium should be employed insubstantial molar excess of the cyclododecatriene-LS ,9. Preferably themolar ratio of lithium to the triene should be in the range of 5:1 to20:1.

After the reaction has been conducted for a desired time such as, forexample, O.520 hours, the reaction mixture is chilled to ice bathtemperature and water is added to hydrolyze the lithium compound. Themixture is then extracted with a suitable solvent to remove the reactionproducts. Extraction with a solvent such as propane or butane removesmainly hydrocarbon material from the reaction mixture, while extractionwith a solvent such as ether removes both hydrocarbon and the aminoproduct. Treatment of the ether extract With dilute HOl Will remove theamino product and neutralization of the resulting aqueous phase withcaustic soda will release the amino product as an oily materiel.Extraction of the neutralized aqueous phase with ether will facilitatethe isolation of the amino product. The product then can be distilled,if desired, to separate the material containing only one ethylenediamine group from higher boiling amino material.

For convenience in the foregoing description the primary diamineemployed has been referred to as ethylene diamine. However the inventioncan also be practiced with other diarnines which will dissolve theirlithium derivatives. Polymet'hylene diamines having 2-6 methylene groupsare suitable generally, examples being propylene diamine andhexamethylene diamine. The number of carbon atoms obtained in the aminoproducts of the reaction 'will depend upon the particular diamineselected.

The intermediate bicyclo hydrocarbon product which reacts to yield theamino derivatives can be characterized as follows. A fraction ofhydrocarbon product distilled from the reaction mixture and boilingsubstantially higher than cyclododecatriene-1,5,9 shows two closeboiling hydrocarbon peaks by vapor phase chromatography. Comparison ofthese peaks with the peaks of a known hydrocarbon mixture used as astandard indicates that the boiling point is about 253 C. at atmosphericpressure. This compares with the normal boiling point forcyclododecatriene-1,5,9 of about 227 C. The isomer designated above as Bis slightly higher boiling than isomer A. Ultraviolet absorption of thehydrocarbon products shows a peak in the neighborhood of 238-244millimicrons and an extinction cocfiicient of about 5500-5600. Byinfrared absorption a carbon-carbon stretching band is found at 6.25microns, which is characteristic for conjugated double bonds. By nuclearmagnetic resonance the ratio of aliphatic protons to vinylic protons isof the order of 8:1 and the ratio of aliphatic protons on carbon atomswhich are alpha to the double bonds to those on carbon atoms which arenon-alpha is about 1:1 for each hydrocarbon product. Thesecharacteristics show that the two hydrocarbon intermediate products havethe structures illustrated in the formulas above.

The amino products, which are obtainable from the reaction mixture byextraction with dilute i-lCl followed by neutralization with causticsoda, can be distilled to separate amino product having only one(w-aminoalkyl) amino group from higher boiling amino material. Themono-addition amino product formed when N-lithio ethylene diamine isused can be obtained as a fraction boiling in the range of 160-175" C.at mm. Hg pressure (the pressure being measured at the receiver ratherthan in the distillation pot). Typically this fraction will also containa substantial amount of hydrocarbon material and hence its nitrogencontent generally will be somewhat lower than the theoretical value forthe monoaddition product. By infrared absorption this fraction shows anitrogen-hydrogen stretching band at about 3.2 microns. Nuclear magneticresonance indicates the presence of one N3 group. it also shows thepresence of allylic hydrogen in an amount indicating one double bond andthe presence of only a small amount of vinylic hydrogen. These factsindicate that this amino product is formed mainly from isomer B byaddition of an ethylene diamine group at one or the carbons adjacent thedouble bond which is not common to the two rings, since addition of onesuch group adjacent either double bond position of isomer A would leavea vinylic proton in the molecule. Also, for isomer B, the double bondwhich is common to the two condensed rings would not be expected toprovide a reactive site for forming the amino compound. Whether theethylene diamine group addition to isomer B occurs at the 2-position or3-position or both is not known with certainty but it seems more likelythat it occurs at least mainly at the 3-position because of sterichindrance. Hence the amino product having one ethylene diamine groupappears likely to conform at least mainly to the following structure:

It should be understood, however, that such structure for themono-addition product is not known with certainty and hence that theproduct cannot be specified in terms of exact structure.

The higher boiling amino product may well be formed by the addition ofan ethylene diamine group at each of the double bond positions of isomerA. However, this is not known with certainty and hence its structurelikewise cannot be specified with exactitude.

The following examples are specific illustrations of the invention:

Example I Three liters of ethylene diamine are heated to a temperatureof about C. and lithium metal is added in amount of g. while the mixtureis being stirred. Reaction between the lithium and the diamine occurswith hydrogen being released, and the mixture is maintained at about 100C. until all of the lithium has reacted. The resulting solution iscolorless. 162 g. of cyclododecatriene-l,5,9 (trans-trans-cis isomer)are then introduced, causing the color of the mixture to turnreddish-brown. The mixture is maintained at a temperature of about 100C. for 2 hours to permit the reaction to proceed. It is then cooled bymeans of an ice bath, and water is mixed into the reaction mixture tohydrolyze the lithium compound. The mixture is then extracted with otherto remove the hydrocarbon and amino products. The resulting ethersolution is extracted with dilute HCl to remove the amino compounds andthen is evaporated to yield a product from which about 18 g. of amixture of the previously described isomers A and B, which distill atabout 66 C. at 2 mm. Hg absolute pressure (receiver pressure), areobtained, leaving 50 g. of residue which is probably a polymer formedfrom the hydrocarbon. By ultraviolet absorption the mixture of isomersis characterized by a peak at 238 millimicrons and an extinctioncoefficient of 5500. By infrared absorption a carbon-carbon stretchingband is found at 6.25 microns, which is characteristic for conjugateddouble bonds.

The HCl extracted amino material is neutralized with caustic soda andextracted with ether. Evaporation of the ether yields 87 grams of aminocompounds. Vacuum distillation of this material produces about 14 g. ofa compound boiling at about 138 C. at 2 mm. Hg absolute pressure(receiver pressure). This product, which is mainly an amino compoundcontaining only one ethylene diamine group, contains about 10.1%nitrogen and shows by infrared absorption a nitrogen-hydrogen stretchingband at about 3.2 microns. The higher boiling material is amino productof higher molecular weight.

Example II The procedure of the preceding example was repeated using 710ml. of ethylene diamine, 35.5 g. of metallic lithium and 38.3 g. oftrans-trans-cis cyclododecatriene- 1,5,9. After addition of the trienethe reaction was again carried out at about 100 C. for a time of 2hours. The reaction product was worked up in a similar manner as before.About 20 g. of hydrocarbon material was obtained of which about one-halfwas unreacted cyclododecatriene. Vacuum distillation of the hydrocarbonmaterial gave about 4 g. of a bicyclo-[5.5.0]-dodecadiene fraction whichdistilled at 85-95 C. at 5 mm. Hg absolute pressure at the receiver and6 g. of dark resinous residue. Vacuum distillation of the amino materialgave about 10 g. of mono-addition product distilling at C. at 5 mm. Hgabsolute pressure at the receiver and 5 g. of higher boiling aminomaterial.

The 85-95 C. fraction analyzed 88.3% C and 11.5% H (theory: 88.9% C,11.1% H). By vapor phase chromatography it showed two peaks indicatingtwo closely boiling hydrocarbons having normal boiling points in thevicinity of 253 C. Material trapped from the chromatograph efiluent andcorresponding to the first peak had a refractive index of 1.5244.Analysis by infrared and ultraviolet absorption and by nuclear magneticresonance showed that these hydrocarbons corresponded to isomers A and Bsupra. The mixture of hydrocarbons by ultraviolet absorption exhibited apeak at 244 millimicrons and an extinction coefficient of 5600, andinfrared showed a carbon-carbon stretching band at 6.25

Nuclear magnetic resonance tests showed promicrons.

ton type ratios consistent with the structures of isomers A and B.

The 160-175 C. fraction of amino material by infrared absorptionexhibited a nitrogen-hydrogen stretching band at 3.2 microns. By nuclearmagnetic resonance this material was shown to have one NI-I group,allylic hydrogen indicative of one double bond and only a small amountof vinylic hydrogen, thus indicating that it was mainly an additionproduct of the diamine reactant with isomer B, with the additionoccurring at the double bond not common to the two condensed rings.

Results similar to those described in the foregoing examples areobtained when other primary aliphatic amines having 3-6 methylene groupsare substituted for the ethylene diamine.

This application is a continuation-in-part of applicants copendingapplication Serial No. 833,380, filed August 13, 1959, now abandoned.

We claim:

1. Method of forming an amino compound which comprises reactingcyclododecatriene-l,5,9 at a temperature in the range of 50-200 C. witha solution of N-lithiopolymethylene diamine having 2-6 methylene groupsdissolved in such polymethylene diamine whereby thecyclododecatriene-1,5,9 rearranges to bicyclo-[5.5.0]-dodecadiene and anamino reaction product between said dodecadiene and the polymethylenediamine is formed, said dodecadiene being characterized by a boilingpoint of about 253 C. at atmospheric pressure, an ultraviolet absorptionpeak at about 238-244 millimicrons and an extinction coeficient of about5500-5600, and separating said amino reaction product from the reactionmixture.

2. Method according to claim 1 wherein the temperature is in the rangeof 80-120 C.

3. An amino compound prepared according to claim 1.

4. Method according to claim 1 wherein said cyclo dodecatriene is thetrans-trans-cis isomer.

5. Method of forming an amino compound which comprises reactingcyclododecatriene-1,5,9 with a solution of N-lithioethylene diamine inethylene diamine at a tem perature in the range of 200 C. whereby thecyclododecatriene-l,5,9 rearranges to bicyclo-[5.5.0]-dodecadiene and anamino reaction product between said dodecadiene and the polymethylenediamine is formed, said dodecadiene being characterized by a boilingpoint of about 253 C. at atmospheric pressure, an ultraviolet absorptionpeak at about 238-244 millimicrons and an extinction coefficient ofabout 5500-5600, and separating said amino reaction product from thereaction mixture.

6. Method according to claim 5 wherein the temperature is in the rangeof -l20 C.

7. Method according to claim 6 wherein said cyclododecatriene is thetrans-trans-cis isomer.

No references cited.

1. METHOD OF FORMING AN AMINO COMPOUND WHICH COMPRISES REACTINGCYCLODODECATRIENE-1,5,9 AT A TEMPERATURRE IN THE RANGE OF 50-200*C. WITHA SOLUTION OF N-LIGHIOPOLYMETHYLENE DIAMINE HAVING 2-6 MMETHYLENE GROUPSDISSOLVED IN SUCH POLYMETHYLENE DIAMINE WHEREBY THECYCLODODECATRIENE-1,5,9 REARRANGES TO BICYCLO-(5.5.0)-DODECADIENE AND ANAMINO REACTION PRODUCT BETWEEN SAID DODECADIENE AND THE POYMETHYLENEDIAMINE IS FORMED SAID DODECADIENE BEING CHARACTERIZED BY A BOILINGPOINT OF ABOUT 253*C. AT ATMOSPHERIC PRESSURE, AN ULTRAVIOLET ABSORPTIONPEAK AT ABOUT 238-244 MILLIMICRONS AND AN EXTINCTION COEFFICIENT OFABOUT 5500-5600, AND SEPARATING SAID AMINO REACTION PRODUCT FROM THEREACTION MIXTURE.